supplementary materials


zl2553 scheme

Acta Cryst. (2013). E69, m398    [ doi:10.1107/S1600536813015870 ]

Poly[(acetonitrile-[kappa]N)-[mu]3-thiocyanato-[kappa]3N:S:S-[mu]2-thiocyanato-[kappa]2N:S-cadmium]

T. Reinert, I. Jess and C. Näther

Abstract top

The asymmetric unit of the title compound, [Cd(NCS)2(CH3CN)]n, consists of one CdII cation, two thiocyanate anions and one acetonitrile ligand, all in general positions. The CdII cation is coordinated by three N atoms of two thiocyanate anions and one acetonitrile ligand, as well as three S atoms of symmetry-related thiocyanate anions within a slightly distorted octahedral coordination environment. The CdII cations are linked by [mu]-1,3(N,S) and [mu]-1,1,3(S,S,N) thiocyanate anions into layers that are located in the ab plane.

Comment top

The structure determination of the title compound was performed as part of a project on the synthesis of new coordination polymers based on transition metal thiocyanates and the investigations on their magnetic properties (Boeckmann et al. (2010, 2011)). Within this project, we have reacted cadmium(II)thiocyanate with 4-tert-butylpyridine in acetonitrile, which resulted in the formation of crystals of the title compound by accident. In the crystal structure the Cd cations are surrounded by three N atoms of two N-bonded µ-1,3-briding thiocyanato anions and one acetonitril ligand as well as three S atoms of three S-bonded µ-1,1,3-bridging thiocyanato anions in a slightly distorted octahedral geometry (Fig. 1 and Tab. 1). The Cd···N distances range from 2.2544 (28) Å to 2.3396 (28) Å, the Cd···S distances from 2.6254 (9) Å to 2.8781 (8) Å (Table 1). The Cd cations are linked into dimeric units by pairs of µ-1,3-briding thiocyanato anions that are further connected into chains by single µ-1,3-briding anionic ligands. These chains are further connected by pairs of µ-1,1,3-bridging thiocyanato anions into layers which are parallel to the crystallographic a-b-plane.

Related literature top

For related structures, see: Wöhlert et al. (2011). For background to transition metal thiocyanate coordination polymers and their magnetic properties, see: Boeckmann et al. (2010, 2011).

Experimental top

The title compound was obtained accidently during the reaction of 68.6 mg Cd(NCS)2 (0.30 mmol) with 11.1 µL 4-tert-butylpyridine (0.08 mmol) in 1.0 ml acetonitrile at RT in a closed 3 ml snap cap vial. After several months colourless blocks of the title compound were obtained.

Refinement top

The H atoms were positioned with idealized geometry, allowed to rotate but not to tip and were refined isotropic with Uiso(H) = 1.5 Ueq(C) of the parent atom using a riding model with C—H = 0.98 Å.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS92 (Sheldrick, 2008); program(s) used to refine structure: SHELXL92 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. : Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: i = -x + 1, -y + 2, -z + 1; ii = x - 1/2, -y + 3/2, -z + 1; iii = -x + 3/2, y - 1/2, z; iv = x + 1/2, -y + 3/2, -z + 1; v = -x + 3/2, y + 1/2, z.
[Figure 2] Fig. 2. : Crystal structure of the title compound with view along the crystallographic c-axis.
Poly[(acetonitrile-κN)-µ3-thiocyanato-κ3N:S:S2-thiocyanato-κ2N:S-cadmium] top
Crystal data top
[Cd(NCS)2(C2H3N)]F(000) = 1024
Mr = 269.61Dx = 2.131 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 22741 reflections
a = 13.0939 (7) Åθ = 1.9–28.2°
b = 8.9752 (5) ŵ = 3.02 mm1
c = 14.2986 (11) ÅT = 200 K
V = 1680.38 (18) Å3Block, colourless
Z = 80.10 × 0.09 × 0.05 mm
Data collection top
STOE IPDS-1
diffractometer
2022 independent reflections
Radiation source: fine-focus sealed tube1943 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
Phi scansθmax = 28.1°, θmin = 3.1°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 1717
Tmin = 0.447, Tmax = 0.799k = 1111
22741 measured reflectionsl = 1818
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.090 w = 1/[σ2(Fo2) + (0.0511P)2 + 2.768P]
where P = (Fo2 + 2Fc2)/3
S = 1.17(Δ/σ)max = 0.001
2022 reflectionsΔρmax = 1.09 e Å3
93 parametersΔρmin = 0.89 e Å3
0 restraintsExtinction correction: SHELXL92 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0100 (7)
Crystal data top
[Cd(NCS)2(C2H3N)]V = 1680.38 (18) Å3
Mr = 269.61Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 13.0939 (7) ŵ = 3.02 mm1
b = 8.9752 (5) ÅT = 200 K
c = 14.2986 (11) Å0.10 × 0.09 × 0.05 mm
Data collection top
STOE IPDS-1
diffractometer
2022 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
1943 reflections with I > 2σ(I)
Tmin = 0.447, Tmax = 0.799Rint = 0.043
22741 measured reflectionsθmax = 28.1°
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.090Δρmax = 1.09 e Å3
S = 1.17Δρmin = 0.89 e Å3
2022 reflectionsAbsolute structure: ?
93 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.580143 (17)0.70475 (2)0.516796 (17)0.02222 (14)
N10.7434 (3)0.7780 (4)0.4831 (2)0.0369 (8)
C10.8127 (2)0.8423 (4)0.4550 (2)0.0248 (6)
S10.91085 (5)0.93385 (8)0.40941 (5)0.02174 (19)
N20.5499 (3)0.9136 (3)0.5999 (2)0.0360 (7)
C20.5257 (2)1.0352 (3)0.6171 (2)0.0264 (6)
S20.49199 (8)1.20580 (8)0.64506 (6)0.0318 (2)
N110.6540 (2)0.5645 (3)0.6370 (2)0.0298 (6)
C110.6836 (2)0.4805 (4)0.6898 (2)0.0271 (6)
C120.7197 (4)0.3726 (5)0.7579 (3)0.0470 (10)
H12A0.68240.27890.75000.070*
H12B0.70830.41130.82110.070*
H12C0.79290.35500.74840.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.01867 (18)0.01728 (18)0.03070 (19)0.00145 (7)0.00221 (7)0.00423 (7)
N10.0250 (16)0.0377 (19)0.048 (2)0.0124 (13)0.0000 (13)0.0006 (13)
C10.0195 (13)0.0244 (14)0.0305 (14)0.0026 (12)0.0042 (11)0.0042 (12)
S10.0181 (3)0.0197 (4)0.0274 (4)0.0017 (2)0.0021 (2)0.0012 (3)
N20.0481 (18)0.0210 (13)0.0388 (15)0.0052 (12)0.0079 (14)0.0011 (12)
C20.0282 (14)0.0249 (14)0.0260 (13)0.0030 (12)0.0053 (11)0.0051 (11)
S20.0458 (5)0.0209 (4)0.0285 (4)0.0052 (3)0.0061 (3)0.0017 (3)
N110.0296 (13)0.0277 (13)0.0322 (13)0.0014 (11)0.0037 (11)0.0020 (11)
C110.0276 (14)0.0254 (14)0.0283 (14)0.0016 (12)0.0055 (12)0.0017 (12)
C120.053 (2)0.039 (2)0.049 (2)0.0052 (17)0.0246 (19)0.0138 (17)
Geometric parameters (Å, º) top
Cd1—N22.254 (3)S1—Cd1v2.8780 (8)
Cd1—N12.287 (4)N2—C21.163 (4)
Cd1—N112.340 (3)C2—S21.643 (3)
Cd1—S2i2.6253 (9)S2—Cd1i2.6253 (9)
Cd1—S1ii2.7522 (8)N11—C111.135 (4)
Cd1—S1iii2.8780 (8)C11—C121.452 (5)
N1—C11.148 (5)C12—H12A0.9800
C1—S11.659 (3)C12—H12B0.9800
S1—Cd1iv2.7523 (8)C12—H12C0.9800
N2—Cd1—N192.08 (13)N1—C1—S1177.3 (3)
N2—Cd1—N1197.64 (11)C1—S1—Cd1iv104.43 (11)
N1—Cd1—N1185.58 (11)C1—S1—Cd1v103.92 (11)
N2—Cd1—S2i98.45 (8)Cd1iv—S1—Cd1v98.29 (2)
N1—Cd1—S2i93.60 (9)C2—N2—Cd1160.0 (3)
N11—Cd1—S2i163.90 (7)N2—C2—S2178.1 (3)
N2—Cd1—S1ii91.84 (9)C2—S2—Cd1i99.62 (11)
N1—Cd1—S1ii164.41 (9)C11—N11—Cd1170.7 (3)
N11—Cd1—S1ii78.95 (7)N11—C11—C12179.1 (4)
S2i—Cd1—S1ii100.74 (3)C11—C12—H12A109.5
N2—Cd1—S1iii172.22 (9)C11—C12—H12B109.5
N1—Cd1—S1iii95.29 (9)H12A—C12—H12B109.5
N11—Cd1—S1iii85.43 (7)C11—C12—H12C109.5
S2i—Cd1—S1iii78.63 (2)H12A—C12—H12C109.5
S1ii—Cd1—S1iii81.71 (2)H12B—C12—H12C109.5
C1—N1—Cd1163.1 (3)
Symmetry codes: (i) x+1, y+2, z+1; (ii) x1/2, y+3/2, z+1; (iii) x+3/2, y1/2, z; (iv) x+1/2, y+3/2, z+1; (v) x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula[Cd(NCS)2(C2H3N)]
Mr269.61
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)200
a, b, c (Å)13.0939 (7), 8.9752 (5), 14.2986 (11)
V3)1680.38 (18)
Z8
Radiation typeMo Kα
µ (mm1)3.02
Crystal size (mm)0.10 × 0.09 × 0.05
Data collection
DiffractometerSTOE IPDS1
diffractometer
Absorption correctionNumerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
Tmin, Tmax0.447, 0.799
No. of measured, independent and
observed [I > 2σ(I)] reflections
22741, 2022, 1943
Rint0.043
(sin θ/λ)max1)0.662
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.090, 1.17
No. of reflections2022
No. of parameters93
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.09, 0.89

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS92 (Sheldrick, 2008), SHELXL92 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top
Cd1—N22.254 (3)Cd1—S1iii2.8780 (8)
Cd1—N12.287 (4)S1—Cd1iv2.7523 (8)
Cd1—N112.340 (3)S1—Cd1v2.8780 (8)
Cd1—S2i2.6253 (9)S2—Cd1i2.6253 (9)
Cd1—S1ii2.7522 (8)
Symmetry codes: (i) x+1, y+2, z+1; (ii) x1/2, y+3/2, z+1; (iii) x+3/2, y1/2, z; (iv) x+1/2, y+3/2, z+1; (v) x+3/2, y+1/2, z.
Acknowledgements top

We gratefully acknowledge financial support by the DFG (project No. NA 720/5–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for the opportunity to use his experimental facility.

references
References top

Boeckmann, J. & Näther, C. (2010). Dalton Trans. 39, 11019–11026.

Boeckmann, J. & Näther, C. (2011). Chem. Commun. 47, 7104–7106.

Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Stoe & Cie (2008). X-SHAPE, X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

Wöhlert, S., Jess, I. & Näther, C. (2011). Acta Cryst. E67, m309.